Photographic elements containing thiazolidine derivatives



1957 G. w. SAWDEY 2,808,330

PHOTOGRAPHIC ELEMENTS CONTAINING THIAZOLIDINE DERIVATIVES Filed Oct. 31, 1952 FILTER LAYER CONTAINING SODIUM SALT OF 3" PHENYL-Z-PHENYUMINO-S- (2- SULFOBENZAL) -4- THIAZOLIDONE GeorgeWSawdey QNVENTOR. I BY N PHOTOGRAPHIC ELEMENTS CONTAINING THIAZOLIDXNE DERIVATIVES George W. Sawdey, Rochester, N.

man Kodak Company, of New Jersey Y., assignor to East- Rochester, N. Y., a corporation This invention relates to new products and new photographic elements proteeted against the harmful effects of ultraviolet radiation.

It is known that certain materials such as cellulosic films and photographic layers, are adversely effected by ultraviolet radiation when such materials are exposed to daylight. In the case of photographic layers, the ultraviolet radiation sometimes causes undesired exposure of the layer, or layers, since photographic silver halide emulsions are sensitive to blue, violet and ultraviolet regions of the spectrum, in addition to any other sensitivity which may be given them, and in the exposure of such material, it is frequently desirable to prevent the action of ultraviolet light on the sensitive emulsion. This is especially true in the case of photographic materials designedfor use in color photography where the film has been sensitized to the longer wavelength regions where it is desirable to record only the rays of the visible spectrum.

Color photographs on multilayer photographic material, particularly where the dye images are formed in sensitive emulsion layers by color development, are susseptible to fading and discoloration by the action of ultraviolet radiation to which the photographs are subjected during viewing. It is also known that the residual couplers contained in the emulsion layers after formation of the picture images in certain processes are attacked by ultraviolet radiation and form a stain which is undesirable in the finished photograph. The action of ultraviolet radiation on finished color photographs is particularly noticeable in positive prints on paper or other opaque supports, since this type of print is frequently viewed in daylight-where there is a high. content of ultraviolet radia tion. This dye fading and yellowing appears to be caused primarily by those wavelengths of light which lie close to the visual region of the spectrum, i. e. 360-400 mil'limicrons.

l have now found that certain new ultraviolet absorbing compounds can be used to overcome the aforementionedv difiiculties, without attendant harmful action by the ultraviolet absorbing compound itself.

- It is," therefore, an object of my invention to provide new compounds and against the harmful effects of ultraviolet radiation. A further object is to provide photographic color materials which have been protectedagainst the harmful effects of ultraviolet radiation. Other objects will becomeappatent from a consideratio'nof the'following description.

I The ultraviolet absorbing compounds which I propose to employ in my invention are advantageously represented by the following general f ormul-a-:' f

wherein R represents a hydrogen atom, an alkyl group photographic elements protected trite States Patent (e. g. methyl, ethyl, propyl, isopropyl, etc.),

2,808,330 ,Pate nted Oct. 1, 1957 or an aryl group (e. g. phenyl, 0-, m-, and p-tolyl, o-, m-', and pch-lorophenyl, etc.), R1 represents an aryl group (e. g. phenyl, o-, m-, propylphenyl, o-, m-, and p-hydroxyphenyl, o-, m-, and p-sulfophenyl (and alkali metal salts thereof, e. g. sodium, potassium, etc.), 4-methoxy-3-sulfophenyl (and alkali metal salts, thereof,. e. .g...sodiu rn, potassium, etc.), 2,4. dicarboxymethoxyphenyl (and alkali. metal salts thereof, e. g. sodium, potassium, etc.), o-, m-, and p-carboxy-' phenyl (and alkali metal salts thereof, e. g. sodium, potassium, etc.), 3-(3-sulfobenzamido)phenyl (and alkali metal salts thereof, e. egsodium, v potassium, etc.), etc.), and Q represents a divalent, non-metallic atom (e. g. oxygen, sulfur, etc.) or radical (e. o-, m-, and p-chlorophenylimino, etc.

The accompanying drawing illustrates schematically a cross-sectional view of a sensitive photographic element having an ultraviolet filter layer containing one of the compounds represented by the above general formula.

These ultraviolet absorbing compounds can. be incorporated in the photographic element in a variety of ways, depending on the ultimate use of the photographic element and the degree of protection desired. Advantageously, the ultraviolet absorbing compound can be dissolved or dispersed in a solvent medium together with a colloidal binder, such as gelatin, cellulose esters (e. g. cellulose acetate, etc.), synthetic resins (e. g. polyvinyl acetals, hydrolyzed polyvinyl acetate, etc.), etc., and

the resulting mixture coatedover the light-sensitive layer of the photographic element. Where the photographic element is a material intended for. use in color photography, the ultraviolet filter layer need not be an outer layer, but this layer. can. be placed over one of the layers subject to the harmful effects of ultraviolet radiation. For example, in a multilayer material comprising three differentially sensitized layers, the red sensitive layer being adjacent to the support, the green sensitive layer being superposed on the red sensitive layer, and the blue sensitive layer being outermost with respect to the other lightsensitive layers, the ultraviolet filter layer can be placed between the blue and green sensitive layers. Alternatively, the ultraviolet filter layer can be placed between the green and the red sensitive layers. If desired, the material useful in absorbing the ultraviolet radiation can be incorporated directly in the light-sensitive emulsion instead of, or in addition to, being present in another layer. The amount of ultraviolet absorbing compound used can be varied, depending upon the effect desired and the use to whichthe material is to-be put.

The Water-soluble compounds of Formula I above (e. g. those containing alkali metal salts of carboxyphenyl, sulfophenyl, etc. groups) can be incorporated into the photographic element by simply bathing the element in an aqueous solution containing the ultraviolet absorbing compound. Where the outer layer contains gelatin, the ultraviolet absorbing compound becomes adsorbed to this layer. By incorporating a resinous mordant, e. g. polyvinyl pyridine methyl p-toluenesulfonate, phenol-formaldehyde ion exchange resins, etc, in the outer gelatin layer (or an intermediate layer where desired), the photographic,

element can be subjected to Washing or processing operations without removal of the ultraviolet absorbing compounds. Thus, the ultraviolet absorbing compounds can be incorporated into the photographic element before or after (i. e. during processing) exposure. The support of the photographic element can be transparent, such as a etc.) support, or a paper support. glass, metal, etc. can be employed,

and p-tolyl, o-, m, and p-anisyl, p-isog. imino, phenylimino,

Formula I which can be used in practicing m comprise those represented by the following formulas:

-p-unisal3-phenyl-2-phenyllmino-4-thiazolidone CoHr-N C=O C QH5N=C CH-C (1H5 s 5-benzal 3-phenyl 2-phenylimino-4-thiazolidone 5-p-methylbenzal-S-phenyI-Z-phenyliminoA-thiazolidone 5-benzal-3-ethylrhodanine C a uN 0:0

N: (E=CHGsHs Ha 3-n-amyl-5-benzal-2-m-tolyliminmbthiazolldone y invention 15. G HaNG=O O=( =0 HC 5H5 5-benzal-3-methyl-2,4-thiazolidinedione 16. CoHsN-G=O CoHrN-C\S C-CH SOJNE. 3-phenyl'2-phenylimino-5-o-sulfi)igenzal-4-thiazolidone (sodium l SOaNa.

5- 4-methoxy-3-sulfobenzal) 3-pl1enyl-2-phenylimi.no-4- thiazolldone (sodium salt) 0 C HAG 0 ONa CaH N-C=O Celia-N O=CH -OOH;OOONa 5- 2,4-dicarboxymethoxybenzal) -3-pheny1-2-phenylimino-4- thiazolidone (sodium salt) wherein R and Q have the values given above, together with an aldehyde of the following general formula:

in. o

Rr-Pl-H wherein R1 has the values given above. Heat accelerates the condensations, temperatures varying from room temperature to the reflux temperature being useful. An inert diluent, e. g. acetic acid, methanol, ethanol, etc. can be used, if desired. Condensing agents, such as piperidine, acetic anhydride, etc. can be employed, if desired.

The compounds of Formula I wherein R1 contains a sulfo or carboxyl group (or alkali metal salts thereof, e. g. sodium, potassium, etc.) are new compounds and are especially useful in the bathing treatment mentioned above. They are useful in the process described in Edgerton and Stand application Serial No. 318,096, filed on even date herewith now U. S. Patent 2,747,996, issued May 29, 1956, being useful either in a layer of the photographic element, or in the bathing solutions disclosed therein. 'The compounds of Formula I can also be added to the photographic silver halide emulsion, though usually less advantageously than when employed in a separate filter layer.

The following examples will serve to illustrate the manner whereby the compounds of Formula I can be prepared.

EXAMPLE 1 3-phenyl-2-phenylimino 5 (o-sulfobenzai) -4-thibz0lidone (sodium salt) COHr-NC=O OoHy-N= =CH OaNa Ana y is;

Calculated for Found flu N fl Percent Percent 57.6 57.4 3.3 3.1 6.1 6.1 13.9 14.1

EXAMPLE 2 5- (4-methorey-3-sulfobenzal) -3-.phenyl-2-ph enylimino- 4-thiazolidone (sodium salt) SFOaNa A mixture of 6.7 g. (0.025 mole) of 3-phenyl-2-phenylimino-4-thiazolidone and 5.5 g. (0.025 mole) of 4-methoxy-3-sulfobenzaldehyde sodium salt in 50 ml. of acetic acid and 5 ml. of acetic anhydride was refluxed under a water-cooled condenser for 8 hours. The cooled reaction mixture was poured into 400 ml. of water, and the solution heated on the steam bath to 85-90" C. The insoluble material was removed by filtration and the filtrate cooled. The solid formed was filtered and washed with 2-25 ml. portions of ice water and crystallized from boiling water. The product was a slightly tan powder, which gave the following analytical results.

Calculated for Found OrsHzrNfzOsSzNa Percent Percent EXAMPLE 3 5- [2,4-bis(carboxymethoxy benzal] -3-phenyl-2- phenylimino-4-thiazolidone (sodium salt) CuHrN= c=on-o onto 0 ONa A mixture of 5.36 g. (0.02 mole) of 3-phenyl-2-phenylimino-4-thiazolidone and 5.46 g. (0.02 mole) of 2,4-biscarbomethomethoxybenzaldehyde in ml. of methyl alcohol containing 3 ml. of piperidine was refluxed for 2 hours. The solid formed was filtered out of the hot solution, washed with 2-25 ml. portions of cold methyl alcohol and crystallized from 200 ml. of acetonitrile. The colorless needle-like product had a melting point of 157- alcoholic alkali. (sodium hydroxide) solution,- and the mixture shaken for several minutes. The dim ethyl ester,

was comp filely hydrolyzed to the above formulated salt. This solution was then used directly for bathing film strips containing a photographic silverhalide layer and a gelatin outercoat.

EXAMPLE 4 3-phenyI-Z-phenylimino-Lidd (3-sulfobenzamido) benzdfl- 4-thiazolid0ne (sodium salt) NH-d- SOsNn A mixture of 5 g. (0.0135 mole) of 5-(3-aminobenzal)- 3-pheny1-2-phenylimino-4athiazolidone and 3.2 g. (0.0135

mole) of m-chlorosulfonylbenzoyl chloride in 100 ml. of dry dioxane was refluxed for 3 hours. The cooled reaction'mixture was poured into 500 ml. of cold water containing 3 g. of sodium acetate and the mixture stirred until the oil first formed solidified; The solid was filtered,

washed with cold water, and dried. Crystallization from acetonitrile gave a light tan powder which decomposed above C. with the evolution of hydrochloric acid gas. The chlorosulfonyl compound thus produced had the following analysis:

Calculated for Found CznHgnClNaO-xS (541) Percent Percent Carbon 64. 0 63. 8 V 3. 7 3. 6 6. 5 6. 4 -7. 7 7. 4 5. 9 5. 8

The 5:[3:(3-chlorosulfonylbenzamido)benzal]-3-phenf yI-Z-phenylimino-4-thiazolidone thus obtained was suspended in an alcoholic alkali (sodium hydroxide) solution, whereupon the desired, above-formulated sodium salt was obtained. The resulting solution was used directly for bathing of film or paper strips having thereon a developed and fixed photographic image.

The 5-(3 aminobenzal) 3 phenyl-2-phenylimino-4- thiazolidone used in the above example was prepared as follows:

A mixture of 6 g. (0.0167 mole) of 5-(3-nitrobenzal)- 3-phenyl-2-phenylimino-4-thiazolidone, 75 ml. of dioxane, 0.5 g. of sodium carbonate and 0.5g. of Raney nickel catalyst was charged into a pressure bottle and shaken on a Parr hydrogenator under 42 pounds of hydrogen pressure at room temperature. After 3 hours the required volume of hydrogen had been absorbed and the bottle was removed from the machine and the solution filtered. The filtrate was evaporated in a vacuum, and the residue crystallized from 50 ml. of acetonitrile. The product obtained (5 g.) was light brown in color, and showed a melting point of 280282 C.

The 3-phenyl 2 phenylimino-5-(3-nitrobenzal)-4-thiazolidone used above was prepared as follows:

A mixture of 13.4 g. (0.05 mole) of 3-phenyl-2-phenylimino-4-thiazolidone, 8.3 g. (0.05 mole) of m-nitrobenzaldehyde, 200 m1. of methyl alcohol and 4.3 ml. of piperidine was refluxed for 3 hours on a steam bath under a water-cooled condenser. The precipitate formed was filtered, washed with cold methyl alcohol, and dried. The bright yellow product was insoluble in most of the common organic solvents; it crystallized difiicultly from boil- -The dimethyl ester thus obtained was suspendedin an 1 ing ethylene glycol. It had a melting point of 22 5-227 C., and gave the following analytical results:

Calculated for Found GnHtsNaOa Percent Percent 65. 7 65. 2 3.7 3. 7 10. 4 10. 3 8. 8. 0

V The following examples will serve to illustrate the application of the compounds of Formula I to photographic elements.

EXAMPLE 5 and gave excellent protection when overcoated on a multilayer paper coating.

' EXAMPLE 6 A multilayer color photographic paper'was exposed and processed, and immediately thereafter immersed for 10 vminutes in a 0.5% aqueous solution of the sodium salt of 3 phenyl 2 phenylamino 5 (2 sulfobenzal)-4- thiazolidone, and dried. Window tests indicated that good protection was thus afforded against the deleterious effect of ultraviolet radiation.

Alternatively, this bath could be applied to protect or to fortify the action of an absorber already incorporated in the material.

In a manner similar tothat illustrated in Examples 4 and 5, photographic elements containing a photographic silver halide emulsion layer can be treated with other ultraviolet absorbing compounds embraced by Formula I above. Where the ultraviolet absorbing compound is not water-soluble, it can be incorporated in the gelatin solution with the aid of an inert solvent, e. g. ethanol, and be uniformly dispersed throughout the gelatin solution before coating.

The accompanying drawing illustrates schematically a cross-sectional view of a photographic element containing a layer having incorporated therein the' sodium salt of 3 phenyl 2 phenylimino 5 (2'- sulfobenzal) 4- thiazolidone, which is representative-of the ultraviolet absorbing agents which can be employed in my invention. 5 As shown in the single figure of the drawing, a support 10 of any suitable material, such as celluloseacetate, or paper, having thereon an emulsion layer 11 is coated with a filterlayer 12 having incorporated therein the sodium salt of 3-phenyl-2-phenylimino-5-(2 sulfobenza1) 4-thiazolidone, or some other ultraviolet absorbing'cornpound selected from those represented by the above general formula (I). It will be understood that the drawing is merely representative of other structures which can be employed in my invention, and that the element can have.

other layers, not shown, such as additional light-sensitive layers, subbing layers, antihalationlayers, etc.

The term an imino group as employed herein includes the simple imino group (HN=) andits substituted de-- rivatives (R2N=, wherein R2 represents an aryl group,

such as those listed above,'for example).

What I claim as my invention and desire secured by I Letters Patent of the United States .is:

l. A finished photographic element comprising a support having thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupled-dye image subject to fading lying between said s'upportand a gelatin layer containing an'ultraviolet absorbing compoundselected from the group consisting of 5-benzal-3-ethylrhodanine and 5-benzal-3-methyl-2,4-thiazolidinedione.

2. A photographic element according to claim 1 wherein the support is a paper support.

References Cited in the file of this patent UNITED sTATEs PATENTS 

1. A FINISHED PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON A PLURALITY OF DEVELOPED AND FIXED PHOTOGRAPHIC EMULSION LAYERS CONTAINING COUPLED-DYE IMAGES, AT LEAST ONE OF SAID DYE IMAGES BEING SUBJECTED TO FADING BY THE ACTION OF ULTRAVIOLET RADIATION, SAID EMULSION LAYER CONTAINING A COUPLER-DYE IMAGE SUBJECTED TO FADING LYING BETWEEN SAID SUPPORT AND A GELATIN LAYER CONTAINING AN ULTRAVIOLET ABSOSRBING COMPOUND SELECTED FROM THE GROUP CONSISTING OF 5-BENZAL-3-ETHYLRHODANINE AND 5-BENZAL-3-METHYL-2,4-THIAZOLIDINEDIONE. 